Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/52—Polymerisation initiated by wave energy or particle radiation by electric discharge, e.g. voltolisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/067—Polyurethanes; Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
  • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2405/00—Adhesive articles, e.g. adhesive tapes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

• the present invention relates to an active energy ray-curable adhesive and a method for producing a laminate.
• film printed materials are laminated with other materials using a laminating adhesive containing a polyisocyanate component and a polyol component, resulting in a laminate that has excellent solvent resistance even to highly polar solvents, and packaging printed materials. is obtained (Patent Document 1).
• these laminating adhesives contain large amounts of organic solvents such as toluene and ethyl acetate during application, a large amount of energy is required for drying the solvent and exhaust treatment, resulting in a large environmental burden.
• an active energy ray-curable adhesive composition which is made by blending an aromatic acrylic acid ester monomer and a resin, and a laminate film is formed by irradiation with an electron beam.
• the active energy ray-curable adhesive composition has a drawback of poor versatility because the films that can be used are limited to product numbers that have an easily adhesive layer.
• the present invention provides a film that instantly cures upon irradiation with active energy rays, exhibits adhesion immediately after irradiation with active energy rays, and exhibits sufficient adhesion even after curing, even to films that do not have an easily adhesive layer.
• the purpose of the present invention is to provide an active energy ray-curable adhesive that can be cured by active energy rays.
• the present invention is an active energy ray-curable adhesive containing a mono- to tetrafunctional (meth)acrylate (A) having a tertiary amino group, a polyol compound (B), and a polyisocyanate compound (C).
• A mono- to tetrafunctional (meth)acrylate
• B polyol compound
• C polyisocyanate compound
• the present invention also provides a step of adhering two or more types of films to each other to form a laminate film via the active energy ray-curable adhesive of the present invention, a step of irradiating the laminate film with active energy rays, and a step of aging.
• This is a method for manufacturing a laminate, including the steps of:
• the active energy ray-curable adhesive of the present invention instantly cures when irradiated with active energy rays, becomes tack-free, shows adhesion even to films without an easily adhesive layer immediately after irradiation with active energy rays, and Sufficient adhesion can be achieved even after curing.
• the active energy ray-curable adhesive of the present invention contains a mono- to tetrafunctional (meth)acrylate having a tertiary amino group.
• the (meth)acrylate will also be referred to as (meth)acrylate (A).
• the (meth)acrylate (A) is cured by irradiation with active energy rays to form a film, and the tertiary amino group strongly interacts with polar groups such as hydroxyl groups, especially carboxyl groups, on the film surface.
• polar groups such as hydroxyl groups, especially carboxyl groups
• the tertiary amino group contained in the (meth)acrylate (A) also functions as a catalyst in the urethane formation reaction between the polyol compound (B) and the polyisocyanate compound (C), which will be described later. It has the effect of promoting this and shortening the curing time. Furthermore, compared to the case where a catalyst is simply present, the (meth)acrylate (A) is cured by active energy rays and is incorporated into the cured film through covalent bonds, so there is an advantage that migration property is low.
• the (meth)acrylate (A) is preferably mono- or difunctional. Furthermore, if the (meth)acrylate (A) has five or more functionalities, the active energy ray-curable adhesive undergoes large curing shrinkage, impairing its adhesion.
• the (meth)acrylate (A) is preferably a compound represented by the following structural formula (1).
• R 1 is H or a methyl group
• R 2 is a monovalent organic group having a (meth)acryloyl group
• R 3 and R 4 are each independently a monovalent hydrocarbon group or a monovalent group containing a heteroatom. Represents an organic group.
• the (meth)acrylate (A) is more preferably a compound represented by the following structural formula (2) or (3).
• R 1 represents H or a methyl group
• R 2 represents a monovalent organic group having a (meth)acryloyl group.
• the (meth)acrylate (A) is preferably a compound represented by the following structural formula (4).
• X represents a nitrogen atom or a carbon atom
• R 1 is H or a methyl group
• R 2 is a monovalent organic group having a (meth)acryloyl group
• R 3 and R 4 are each independently a monovalent carbonized Represents a monovalent organic group containing a hydrogen group or a heteroatom.
• R 3 and R 4 are independent of each other or together form a cyclic group.
• the amine value of the (meth)acrylate (A) is preferably 80 mgKOH/g or more in order to strongly interact with various carboxyl groups and improve adhesion. Further, in order to impart compatibility with other compounds, the amine value of the (meth)acrylate (A) is preferably 400 mgKOH/g or less, more preferably 357 mgKOH/g or less.
• the amine value is expressed as the number of mg of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize the amino groups contained in 1 g of the sample, and can be measured by a method compliant with ASTM D2074. .
• the (meth)acrylate (A) has a hydroxyl group. By doing so, it can be added to the polyisocyanate compound (C) described below to more effectively improve curability and adhesion.
• the (meth)acrylate (A) can be obtained by subjecting a polyfunctional (meth)acrylate to a Michael addition reaction with primary or secondary amines. Since the (meth)acryloyl group is an ⁇ - ⁇ unsaturated carbonyl compound, a 1,4-conjugate addition of primary or secondary amines results in a 3-aminopropionate structure. If the amino group in the structure after the reaction is secondary, there is a possibility that it will be reacted once more and converted to a tertiary amine. Furthermore, this reaction is a nucleophilic reaction, and the higher the nucleophilicity, the milder the conditions will be. In addition, acids and bases act as catalysts, making it possible to proceed at lower temperatures and higher speeds.
• the reaction When specifically carrying out the Michael addition reaction, it is preferable to carry out the reaction at a temperature of 20 to 100°C or lower.
• the equivalent ratio is More preferably, it is in excess.
• the (meth)acrylate (A) has a hydroxyl group
• a polyfunctional (meth)acrylate is used as a raw material for the Michael addition reaction, since it is necessary for the (meth)acryloyl group to remain after the reaction.
• Monofunctional (meth)acrylates are unsuitable because Michael addition eliminates the (meth)acryloyl group.
• examples include acrylate, isocyanuric acid tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ethylene oxide adducts, propylene oxide adducts, and tetraethylene oxide adducts of these.
• Examples of the (meth)acrylates having five or more functional functions as raw materials for the Michael addition reaction include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide adducts and propylene oxide adducts thereof. etc.
• primary amines serving as raw materials for the Michael addition reaction include monoamines such as alkylamines having 1 to 20 carbon atoms, alkanolamines having 1 to 10 carbon atoms, and derivatives thereof.
• secondary amines include N-alkyl substituted products of the above monoamines (having 1 to 20 carbon atoms), N-alkanol substituted products of the above monoamines (having 1 to 10 carbon atoms), morpholine, pyrrolidine, piperidine, etc.
• Cyclic amines derivatives other than those substituted with N, 1H-azoles such as 1H-triazole, 1H-benzotriazole, 1H-benzimidazole, 1H-imidazole, 1H-pyrazole, and derivatives substituted with other than 1H are Can be mentioned. These polyamines can also be used, but in that case, control is required to suppress gelation.
• amines with low odor are preferred, and octadecylamine and diethanolamine are particularly preferred because they are raw materials that can be used in food packaging regulations such as the Swiss Ordinance.
• adducts of 1H-azoles having a heterocycle such as 1H-triazole, 1H-benzotriazole, 1H-benzimidazole, and 1H-imidazole, are particularly preferred because of their great adhesion-improving effect.
• aliphatic amines with high nucleophilicity undergo a Michael addition reaction under relatively mild conditions of 20 to 60°C.
• the reaction of aromatic amines with low nucleophilicity progresses slowly, and the Michael addition reaction is preferably carried out by heating to 80 to 100°C.
• the (meth)acrylate (A) When the (meth)acrylate (A) is synthesized using the particularly preferred diethanolamine listed above, it becomes a compound represented by the above structural formula (2), and the (meth)acrylate (A) is synthesized using octadecylamine. When synthesized, it becomes a compound represented by the above structural formula (3). Furthermore, when the (meth)acrylate (A) is synthesized using 1H-azoles, it becomes a compound represented by the above structural formula (4).
• (meth)acrylate (A) commercially available products may be used, such as "EBECRYL” (registered trademark) LEO 10101, “EBECRYL” (registered trademark) LEO 10551, and “EBECRYL” manufactured by Daicel Allnex.
• EBECRYL registered trademark LEO 10101
• EBECRYL registered trademark LEO 10551
• EBECRYL manufactured by Daicel Allnex.
• the (meth)acrylate (A) is preferably contained in the active energy ray-curable adhesive in an amount of 10% by mass or more and 40% by mass or less.
• Film adhesion is improved when the content of the (meth)acrylate (A) is 10% by mass or more, more preferably 20% by mass or more.
• the content of the (meth)acrylate (A) is 40% by mass or less, other functional materials may be included depending on the application, or an initiator and sensitizer may be added depending on the active energy ray source. In this case, resins, oligomers, auxiliary agents, etc. can be added to adjust the viscoelasticity of active energy ray-curable adhesives.
• the active energy ray-curable adhesive of the present invention contains a polyol compound (B).
• the polyol compound (B) refers to a compound having two or more hydroxyl groups.
• polyol compound (B) examples include neopentyl glycol, 1,3-butanediol, 1,4-butanediol, tripropylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane. , diglycerin, dipentaerythritol, ethylene oxide adduct, propylene oxide adduct, tetraethylene oxide adduct, lactone adduct, and the like.
• the polyol compound (B) is a polyester polyol, since it can improve the heat resistance of the active energy ray-curable adhesive and impart resistance to boiling and retort treatment.
• the polyester structure in the polyester polyol is obtained by reacting a dicarboxylic acid derivative with a diol.
• dicarboxylic acid derivatives include phthalic acid, isophthalic acid, terephthalic acid, adipic acid, oxalic acid, maleic acid, fumaric acid, and sebacic acid. These can be reacted with diols to form a polyester structure, and a polyester polyol having a hydroxyl group at the terminal can be used.
• polyol compounds having a carbonate structure can also be used. Specific examples include pentamethylene carbonate diol, hexamethylene carbonate diol, hexane carbonate diol, decane carbonate diol, and the like. Moreover, these polyol compounds can be used alone or in combination of two or more.
• the molecular weight of the polyol compound (B) is preferably 500 or more, more preferably 1000 or more, and even more preferably 2000 or more, from the viewpoint of improving adhesion by increasing the molecular weight.
• the molecular weight of the polyol compound (B) is preferably 10,000 or less, more preferably 7,000 or less, and even more preferably 5,000 or less, from the viewpoint of increasing the fluidity of the adhesive and improving the coating properties.
• the active energy ray-curable adhesive of the present invention contains a polyisocyanate compound (C).
• the polyisocyanate compound (C) refers to a compound having two or more isocyanate groups, and is a component whose molecular weight is increased by an addition reaction.
• polyurethane is formed by mixing and reacting the polyol compound (B) and the polyisocyanate compound (C).
• the tertiary amino group contained in the (meth)acrylate (A) also functions as a catalyst, which has the effect of promoting the reaction and shortening the curing time. Furthermore, compared to the case where a catalyst is simply present, the (meth)acrylate (A) is cured by active energy rays and is incorporated into the cured film through covalent bonds, so there is an advantage that migration property is low.
• polyisocyanate compound (C) examples include toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4-methylenebiscyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, and hexyl diisocyanate. Examples include methylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and the like. Nurate modified products, adduct modified products, biuret modified products, allophanate modified products, etc. of these polyisocyanate compounds can also be used. These diisocyanates may be used alone or in combination of two or more.
• the weight average molecular weight of the polyisocyanate compound (C) is preferably 500 or more, more preferably 1000 or more, and even more preferably 2000 or more, from the viewpoint of suppressing elution when remaining in the cured adhesive.
• the weight average molecular weight of the polyisocyanate compound (C) is preferably 10,000 or less, more preferably 7,000 or less, and even more preferably 5,000 or less, from the viewpoint of increasing the fluidity of the adhesive and improving the coating properties.
• the total content of the polyol compound (B) and the polyisocyanate compound (C) in the active energy ray-curable adhesive of the present invention improves the adhesion of the final laminate film, and further improves the adhesiveness of the final laminate film.
• the content is preferably 50% by mass or more, more preferably 60% by mass or more.
• the amount is preferably 80% by mass or less, more preferably 70% by mass or less.
• the equivalent ratio of the polyol compound (B) and the polyisocyanate compound (C) is such that the content of isocyanate groups in the polyisocyanate compound is 0.8 mol to 1.0 mol of hydroxyl groups in the polyol compound (B).
• the amount is preferably 1.2 mol or less.
• the polyol compound it is preferable that the content of isocyanate groups in the isocyanate compound is 0.8 mol or more and 1.2 mol or less. The closer the equivalent ratio is, the more the chain elongation reaction progresses, the higher the molecular weight of the resulting polyurethane, and the better the adhesion.
• the active energy ray-curable adhesive of the present invention preferably has a weight average molecular weight of less than 3000 and also contains a polyfunctional (meth)acrylate that does not contain an amino group.
• the (meth)acrylate will also be referred to as (meth)acrylate (D).
• the (meth)acrylate (D) is cured by irradiation with active energy rays and contributes to film formation.
• the (meth)acrylate (D) is preferably one with high reactivity from the viewpoint of curability. Furthermore, from the viewpoint of safety and the environment, it is preferable that the volatility is low. Low volatility refers to a weight loss rate of 1% by weight or less when heated at 110°C for 1 hour, as defined by Method 24 of the US Environmental Protection Agency (EPA).
• EPA US Environmental Protection Agency
• examples of difunctional (meth)acrylates (D) include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di( meth)acrylate, 1,10-decanediol di(meth)acrylate, bisphenol A di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene Glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate Acrylate, pentaerythritol di(meth)acrylate, diglycerin di(meth)acrylate, ditri
• Examples of the trifunctional (meth)acrylate (D) include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, and isocyanuric acid.
• Examples include tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and ethylene oxide adducts, propylene oxide adducts, and tetraethylene oxide adducts thereof.
• Examples of the tetrafunctional (meth)acrylate (D) include ditrimethylolpropane tetra(meth)acrylate, diglycerintetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethylene oxide adducts thereof, and propylene oxide. Examples include adducts and the like.
• the active energy ray-curable adhesive of the present invention preferably contains a compound having a carboxyl group with a weight average molecular weight of 3,000 or more and 100,000 or less.
• the compound will also be referred to as compound (E).
• the tertiary amino group of the (meth)acrylate (A) interacts with the carboxyl group of the high molecular weight compound (E), improving the film formability and film strength of the active energy ray-curable adhesive cured film.
• n c (E)/n a (A) 0.50 or less, more preferably 0.30 or less, and still more preferably 0.15 or less
• the tertiary amino group and the polar group on the film surface can be It is possible to effectively improve adhesion due to the interaction of the two.
• the compound (E) preferably has a (meth)acryloyl group and/or a vinyl group. Since the compound (E) also interacts with the (meth)acrylate (A) and crosslinks, the compound (E) having the above-mentioned photosensitive group improves the curability to active energy rays. This also improves the strength and adhesion of the cured film.
• the active energy ray-curable adhesive of the present invention may contain a photopolymerization initiator depending on the active energy ray source.
• a photopolymerization initiator for example, ⁇ -aminoalkylphenones, thioxanthones, benzyl ketals, and acylphosphine oxides can be used.
• the active energy ray-curable adhesive of the present invention may contain additives such as wax, pigment dispersant, antifoaming agent, leveling agent, etc. as other components.
• the active energy ray-curable adhesive of the present invention is substantially free of solvents and diluents.
• solvent refers to a solvent that does not contain a (meth)acryloyl group and is liquid at 1 atm and 25°C.
• substantially free of solvent and diluent means that the total content of the solvent and diluent in the active energy ray-curable adhesive is 0.1% by mass or less. Since the active energy ray curable adhesive of the present invention does not substantially contain a solvent, the curability of the adhesive against active energy rays can be improved. Further, it is possible to prevent the solvent from passing through the printing film and transferring to the contents.
• the acrylic equivalent of the active energy ray-curable adhesive of the present invention is preferably 300 g/eq or more and 1000 g/eq or less. Storage stability is improved because the acrylic equivalent is 300 g/eq or more, more preferably 500 g/eq or more. Further, when the acrylic equivalent is 1000 g/eq or less, more preferably 800 g/eq or less, curability with active energy rays becomes good. In the present invention, the acrylic equivalent is the number of grams (unit: :g/eq).
• the active energy ray-curable adhesive of the present invention comprises the (meth)acrylate (A), the polyol compound (B), the polyisocyanate compound (C), and, if necessary, the (meth)acrylate (D). , the above compound (E), and other components at room temperature to 80°C.
• defoaming is also preferably carried out under vacuum or reduced pressure conditions.
• a first aspect of the method for producing a laminate of the present invention includes a laminating step in which the same type or two or more types of films are bonded to each other to form a laminate film via the active energy ray-curable adhesive of the present invention;
• the method includes, in this order, an irradiation step of irradiating the laminate film with active energy rays, and an aging step of aging the laminate film.
• a laminate film is obtained by applying the active energy ray-curable adhesive of the present invention onto one of the films and laminating the other film onto the wet coating film.
• one film is a printed matter printed with ink
• the other film is a sealant.
• a second aspect of the method for producing a laminate of the present invention includes a step of applying an active energy ray-curable adhesive to a film, an irradiation step of irradiating the film coated with the adhesive with active energy rays, and a step of applying an active energy ray-curable adhesive to the film.
• the process includes, in this order, a laminating process in which films of the same or different types are adhered to the coated film to form a laminate film, and an aging process in which the film is aged.
• Examples of the film used in the present invention include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyester such as polylactic acid, polyamide, polyimide, polyalkyl (meth)acrylate, polystyrene, poly ⁇ -methylstyrene, polycarbonate, polyvinyl Examples include alcohol, polyvinyl acetal, polyvinyl chloride, and polyvinylidene fluoride.
• films in which these films further have a vapor-deposited thin film layer made of a metal such as alumina or a metal compound.
• the surface of the film is preferably corona-treated, since the number of polar functional groups on the film surface increases and the adhesion to the active energy ray-curable adhesive is improved. Further, when the film is a printed matter, it is preferable that the surface of the plain portion thereof is subjected to corona treatment.
• the film whose surface has been corona-treated may be a ready-made product, or it may be one in which the film is subjected to in-line corona treatment before printing or lamination.
• the active energy ray-curable adhesive of the present invention is suitable because it can exhibit sufficient adhesion even to films without an easily adhesive layer.
• either sheet or roll film can be used.
• a roll film When using a thin film for flexible packaging, it is preferable to use a roll film and perform coating and printing in a roll-to-roll manner.
• the active energy ray curable adhesive is instantly cured by reacting the (meth)acryloyl group with the active energy ray irradiation and crosslinking with covalent bonds.
• Examples of the active energy ray source used in the irradiation step include ultraviolet rays, electron beams, and gamma rays.
• ultraviolet irradiation devices such as high-pressure mercury lamps, xenon lamps, metal halide lamps, and light emitting diodes (LEDs) are preferably used.
• LED lamps are preferred because they are energy efficient and generate less ozone.
• the wavelength of the LED a bright line of 350 to 420 nm is preferable from the viewpoint of power saving and cost reduction.
• the (meth)acryloyl group is directly radically excited, and radical polymerization proceeds in the active energy ray-curable adhesive to form a film.
• electron beams have high transparency and can act on films as well.
• the film is polyolefin, radicals are easily generated, causing reactions such as crosslinking and decomposition between molecules, and radical polymerization progresses between the active energy ray curable adhesive and the film, resulting in active energy ray curable adhesive.
• a covalent bond is formed between the agent/film and higher adhesion can be developed.
• electron beams with low accelerating voltages are preferred because they require no special qualifications and are easy to handle.
• the accelerating voltage is preferably 50 kV to 300 kV from the viewpoint of sufficient transparency and damage to the film.
• the irradiation dose of the electron beam is preferably 10 kGy or more and 100 kGy or less, since the amount of radical species generated in the target substance increases and the damage to the film also increases.
• the reaction between the polyol compound (B) and the polyisocyanate compound (C) in the adhesive proceeds by heat treatment in an environment of 40°C or more and 60°C or less, and the molecular weight decreases. By increasing the amount, adhesion can be further improved.
• Weight average molecular weight is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase at a column temperature of 40°C.
• the column used was Shodex KF-803, and the weight average molecular weight was calculated in terms of polystyrene.
• the peel strength of the sample immediately after curing with active energy rays was evaluated as "initial adhesion.”
• the peel strength of the sample after aging at 40° C. for 72 hours (after curing) was evaluated as "adhesion after curing.”
• the peel strength is less than 1.0N/15mm, the adhesion is insufficient, and if it is 1.0N/15mm or more and less than 2.0N/15mm, the adhesion is good, and 2.0N/15mm or more and less than 2.0N/15mm is good. /15 mm or more was judged to be extremely good.
• Weight average molecular weight 360 (A)-2: Di(2-ethylhexyl)amine (manufactured by Wakenyaku Co., Ltd.) was added to ditrimethylolpropane tetraacrylate (“Miramer” (registered trademark) M410, manufactured by MIWON) in an equivalent ratio of 2:1. Di- to trifunctional (meth)acrylate subjected to addition reaction. No hydroxyl groups. Amine value: 118 mgKOH/g. Weight average molecular weight 590.
• (A)-4 Michael addition reaction of octadecylamine (manufactured by TCI Corporation) to tricyclodecane dimethanol diacrylate (“EBECRYL” (registered trademark) 130, manufactured by Daicel Allnex Corporation) at an equivalent ratio of 2:1. and mono- or di-functional (meth)acrylates. No hydroxyl groups. Amine value: 96 mgKOH/g. Weight average molecular weight 420.
• (A)-5 Dimethylaminoethyl methacrylate (manufactured by TCI Corporation).
• (A)-5 is a monofunctional (meth)acrylate. No hydroxyl groups. Amine value: 357 mgKOH/g. Weight average molecular weight 160.
• (A)-7 Pentaerythritol triacrylate (“Miramer” (registered trademark) M340 manufactured by MIWON) and dimethylaminoethyl methacrylate (manufactured by TCI Corporation) were mixed with polyetheramine ( A mono- to tri-functional (meth)acrylate obtained by subjecting HUNTSMAN's "JEFFAMINE” (registered trademark) D-2000) to a Michael addition reaction. Contains hydroxyl group. Amine value: 91 mgKOH/g. Weight average molecular weight 3200.
• (E)-1 Acrylic resin having a photosensitive group and a carboxylic acid (TWR-1001 manufactured by Toray Industries, Inc.). Molecular weight 30,000, acid value 105mgKOH/g.
• (E)-2 Acrylic resin containing carboxylic acid (TWR-3001 manufactured by Toray Industries, Inc.). Molecular weight 27000, acid value 200mgKOH/g.
• Photopolymerization initiator bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide (“Irgacure” (registered trademark) 819 manufactured by BASF)
• Solvent Ethyl acetate (manufactured by Wakeyaku Co., Ltd.).
• Film 1 12 ⁇ m thick PET film (E5102 manufactured by Toyobo Co., Ltd.) with a corona treatment layer.
• Film 2 12 ⁇ m thick PET film (FS2000 manufactured by Futamura Chemical Co., Ltd.), without surface treatment.
• Film 3 Polyamide film (ON manufactured by Unitika Co., Ltd.) with a thickness of 15 ⁇ m, with a corona treatment layer.
• Film 4 Barrier film/PET film laminate (1011HG SBR2 manufactured by Toray Film Processing Co., Ltd.) with a thickness of 12 ⁇ m, without a corona treatment layer.
• Film 5 20 ⁇ m thick OPP film (P2111 manufactured by Toyobo Co., Ltd.) with a corona treatment layer.
• Film 6 PET film with a thickness of 12 ⁇ m (“Lumirror” (registered trademark) S10 manufactured by Toray Industries, Inc.), without surface treatment.
• Method for manufacturing laminate 1 After applying various active energy ray-curable adhesives to various films at a coating amount of approximately 2.0 g/m 2 , a sealant (unoriented polypropylene film (CPP)) (Toray Film Processing Co., Ltd. ZK-207 (manufactured by ), thickness 60 ⁇ m) was laminated. Then, using an electron beam irradiation device (EC250/30/90LS manufactured by Iwasaki Electric Co., Ltd.), the substrate was irradiated with an electron beam at an acceleration voltage of 110 kV and an irradiation dose of 30 kGy. The adhesive was cured by starting from the film side.Then, it was cured at 40°C for 72 hours.
• CPP unoriented polypropylene film
• Example 1 A laminate was produced by laminate manufacturing method 1 using active energy ray curable adhesive 1 as the active energy ray curable adhesive and film 1 as the film. Regarding the peel strength, the initial adhesion was also good at 1.8 N/15 mm, and the adhesion after curing was also extremely good at 4.5 N/15 mm. The failure mode was also good (A), and the appearance of the coated product was also good. The results are shown in Table 2.
• Examples 2 to 15 and Comparative Examples 1 to 3 A laminate was produced by laminate manufacturing method 1 using active energy ray curable adhesives 2 to 15 and 17 to 19 as active energy ray curable adhesives and film 1 as the film.
• the peel strength was all better than good.
• Example 16-20 A laminate was produced by laminate production method 1 using active energy ray curable adhesive 1 as the active energy ray curable adhesive and films 2 to 6 as the film. As for the peel strength, both the initial adhesion and the adhesion after curing were more than good, and the results were particularly good for the corona-treated film. The results are shown in Table 3.
• Examples 21 and 22 A laminate was produced by UV curing according to laminate manufacturing method 2 using active energy ray curable adhesive 16 as the active energy ray curable adhesive and films 1 and 2 as the films. For both films, the peel strength was good or better for both the initial adhesion and the adhesion after curing, and especially for film 1 which was subjected to corona treatment, it was extremely good. The results are shown in Table 3.
• Example 23 and 24 A laminate was produced by laminate manufacturing method 3 using active energy ray curable adhesive 1 as the active energy ray curable adhesive and films 2 and 4 as the films. Corona treatment improved both initial adhesion and post-curing adhesion for both films, and the lamination peel strength was extremely good. The results are shown in Table 3.
• Example 25 A laminate was produced by laminate production method 4 using active energy ray curable adhesive 1 as the active energy ray curable adhesive and film 4 as the film. By performing electron beam irradiation before lamination, initial adhesion was improved by accelerating curing. The final laminate peel strength was comparable to that of Example 18, which was a good result. The results are shown in Table 3.

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• 2023
  • 2023-06-22 WO PCT/JP2023/023113 patent/WO2024004817A1/ja not_active Ceased
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